Detection of ClCO with time-resolved Fourier-transform infrared absorption spectroscopy

ClCO was produced as a reaction intermediate after irradiation of a flowing mixture of Cl2/CO/Ar at 355 nm. A step-scan time-resolved Fourier-transform infrared spectrometer operated in absorption mode was employed to detect ClCO. A transient spectrum at a resolution of 0.13 cm−1 partially reveals rotational structure with the Q-branch peaked at 1884.59 cm−1; the transition is associated with the C–O stretching (ν1) mode of ClCO. Calculations with density-functional theory (B3LYP/aug-cc-pVTZ) predict the geometry, vibrational and rotational parameters of 35ClCO and 37ClCO. A simulated absorption spectrum based on these parameters agrees satisfactorily with experimental observation.